1. Field of the Invention
This invention relates to the recovery of oxygenated organic compounds from dilute aqueous solutions by selective sorption and is especially applicable to the dilute aqueous ethanol obtained from fermentation.
2. Description of the Prior Art
With the ever-increasing depletion of economically recoverable petroleum reserves, the production of ethanol from vegetative sources as a partial or complete replacement for conventional fossil-based liquid fuels becomes more attractive. In some areas, the economic and technical feasibility of using a 90% unleaded gasoline-10% anhydrous ethanol blend ("gasohol") has shown encouraging results. According to a recent study, gasohol powered automobiles have averaged a 5% reduction in fuel compared to unleaded gasoline powered vehicles and have emitted one-third less carbon monoxide than the latter. In addition to offering promise as a practical and efficient fuel, biomass-derived ethanol in large quantities and at a competitive price has the potential in some areas for replacing certain petroleum-based chemical feedstocks. Thus, for example, ethanol can be catalytically dehydrated to ethylene, one of the most improtant of all chemical raw materials both in terms of quantity consumed and versatility in product synthesis.
The various operations in processes for obtaining ethanol from such recurring sources as cellulose, cane sugar, amylaceous grains and tubers, e.g., the separation of starch granules from non-carbohydrate plant matter and other extraneous substances, the chemical and/or enzymatic hydrolysis of starch to fermentable sugar (liquefaction and saccharification), the fermentation of sugar to a dilute solution of ethanol ("beer") and the separation and concentration of the ethanol by distillation, have been modified in numerous ways to achieve improvements in product yield, production rates and so forth (see, for example, U.S. Pat. No. 3,236,740 and the booklet "Industrial Alcohol by Continuous Fermentation and Vacuum Distillation With Low Energy Consumption", of Chemapec, Inc., Woodbury, N.Y.). For ethanol to realize its vast potential as a partial or total substitute for petroleum fuels or as a substitute chemical feedstock, it is necessary that the manufacturing process be as efficient in the use of energy and raw materials as possible so as to maximize the energy return for the amount of ethanol produced and enhance the standing of the ethanol as an economically viable replacement for petroleum based raw materials. To date, however, relatively little concern has been given to the energy and raw material requirements for manufacturing ethanol from biomass and consequently, little effort has been made to minimize the thermal expenditure and waste of raw materials incurred in carrying out any of the aforesaid discrete operations involved in the manufacture of ethanol from vegetative sources.
Recovery of fermentation ethanol by distillation accounts for a large amount of the overall energy requirements for conversion of biomass to concentrated ethanol. Berry, "Distribution of Ethanol-Water Mixtures to Organic Liquids" Ind. Eng. Process Des. Dev. 1981, 20, 104-108 describes attempts to use solvent extraction as a substitute for distillation in alcohol separation and concentration. According to this publication, the hydrocarbons as a class are poor extractants for ethanol, but tend to give the highest separation factors because of their even poorer solvent properties for eater. A variety of solvents, each of them liquid, are evaluated in this publication including cyclohexane, benzene, toluene, xylene, ethybenzene, chloroform, 1-octanol, n-butyl acetate and tri-n-butyl phosphate.
While it is known from Japanese Patent Publication J50639-025 that crosslinked polyvinylpyridine resin is useful for separating phenolic compounds such as phenol, cresol, ethylphenol, naphthol, catechol, resorcinol, hydroquinone or their derivatives, there is no suggestion in this disclosure that resins of this type may also be useful for the preferential adsorption of ethanol from a dilute aqueous ethanol stream.
Similarly, other oxygenated organic materials are obtained in chemical, biochemical and fermentation processes in dilute aqueous solutions and their efficient recovery is desirable to a commercial process. Exemplary of such oxygenated organic materials comprise alcohols, aldehydes, ketones, ethers, acids, esters and the like.